High chloride emulsion doped with combination of metal complexes

ABSTRACT

A radiation-sensitive emulsion comprised of high chloride silver halide grains having a central portion accounting for up to 99 percent of total silver and containing a first dopant of Formula (I): [RuL 6 ] n  wherein n is −2, −3 or −4, and L 6  represents bridging ligands which can be independently selected, provided that at least four of the ligands are anionic ligands, and at least one of the ligands is a cyano ligand or a ligand more electronegative than a cyano ligand; and a second dopant comprising an iridium coordination complex having ligands each of which are more electropositive than a cyano ligand; wherein the first dopant and the second dopants are located together in a common dopant band in an interior shell region of the central portion of the silver halide grains that surrounds at least 70 percent of the silver and, with the more centrally located silver, accounts for 90 percent of the silver halide forming the grains, and wherein the second dopant is present in the silver halide grains in a concentration of at least 10 −7  mole/mole of total silver. The combination of first and second dopants in a common dopant band provides greater reduction in reciprocity law failure than is achieved with such dopants in separate bands, and also provides improvements in speed and contrast properties.

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application is a continuation-in-part of U.S. Ser. No. 09/919,001, filed Jul. 31, 2001, the disclosure of which is incorporated by reference herein.

FIELD OF THE INVENTION

[0002] This invention is directed to radiation sensitive silver halide emulsions useful in photography, including electronic printing methods wherein information is recorded in a pixel-by-pixel mode in a radiation silver halide emulsion layer, comprising a combination of specified classes of dopants.

[0003] Definition of Terms

[0004] The term “high chloride” in referring to silver halide grains and emulsions indicates that chloride is present in a concentration of greater than 50 mole percent, based on total silver.

[0005] In referring to grains and emulsions containing two or more halides, the halides are named in order of ascending concentrations.

[0006] All references to the periodic table of elements periods and groups in discussing elements are based on the Periodic Table of Elements as adopted by the American Chemical Society and published in the Chemical and Engineering News, Feb. 4, 1985, p. 26. The term “Group VIII” is used to generically describe elements in groups 8, 9 and 10.

[0007] The term “cubic grain” is employed to indicate a grain is that bounded by six {100} crystal faces. Typically the corners and edges of the grains show some rounding due to ripening, but no identifiable crystal faces other than the six {100} crystal faces. The six {100} crystal faces form three pairs of parallel {100} crystal faces that are equidistantly spaced.

[0008] The term “cubical grain” is employed to indicate grains that are at least in part bounded by {100} crystal faces satisfying the relative orientation and spacing of cubic grains. That is, three pairs of parallel {100} crystal faces are equidistantly spaced. Cubical grains include both cubic grains and grains that have one or more additional identifiable crystal faces. For example, tetradecahedral grains having six {100} and eight {111} crystal faces are a common form of cubical grains.

[0009] The term “tabular grain” indicates a grain having two parallel major crystal faces (face which are clearly larger than any remaining crystal face) and having an aspect ratio of at least 2.

[0010] The term “aspect ratio” designates the ratio of the equivalent circular diameter of a major face to grain thickness.

[0011] The term “tabular grain emulsion” refers to an emulsion in which tabular grains account for greater than 50 percent of total grain projected area.

[0012] The term “{100} tabular” is employed in referring to tabular grains and tabular grain emulsions in which the tabular grains have {100} major faces.

[0013] The term “equivalent spherical diameter” in referring to silver halide grains refers to the diameter of a sphere which has the same volume of an individual grain.

[0014] The term “central portion” in referring to silver halide grains refers to that portion of the grain structure that is first precipitated accounting for up to 99 percent of total precipitated silver required to form the grains.

[0015] The term “dopant” is employed to indicate any material within the rock salt face centered cubic crystal lattice structure of a silver halide grain other than silver ion or halide ion.

[0016] The term “dopant band” is employed to indicate the portion of the grain formed during the time that dopant was introduced to the grain during precipitation process.

[0017] The term “surface modifier” refers to any material other than silver ion or halide ion that is associated with a portion of the silver halide grains other than the central portion.

[0018] The term “log E” is the logarithm of exposure in lux-seconds.

[0019] Speed is reported as relative log speed, where 1.0 relative log speed units is equal to 0.01 log E.

[0020] The term “contrast” or ‘γ’ is employed to indicate the slope of a line drawn from stated density points on the characteristic curve.

[0021] The term “reciprocity law failure” refers to the variation in response of an emulsion to a fixed light exposure due to variation in the specific exposure time.

[0022]Research Disclosure is published by Kenneth Mason Publications, Ltd., Dudley House, 12 North St., Emsworth, Hampshire P010 7DQ, England.

BACKGROUND

[0023] In its most commonly practiced form silver halide photography employs a film in a camera to produce, following photographic processing, a negative image on a transparent film support. A positive image for viewing is produced by exposing a photographic print element containing one or more silver halide emulsion layers coated on a reflective white support through the negative image in the camera film, followed by photographic processing. Whereas high bromide silver halide emulsions are the overwhelming commercial choice for camera films, high chloride grain emulsions are the overwhelming commercial choice for photographic print elements. In a relatively recent variation negative image information is retrieved by scanning and stored in digital form. The digital image information is later used to expose imagewise the emulsion layer or layers of the photographic print element. Whether a conventional optical or a digital image printing exposure is employed, it is desired in high chloride emulsions for color paper applications to obtain high photographic speed at the desired sensitometric curve shape.

[0024] A typical example of imaging systems which require that a hard copy be provided from an image which is in digital form is electronic printing of photographic images which involves control of individual pixel exposure. Such a system provides greater flexibility and the opportunity for improved print quality in comparison to optical methods of photographic printing. In a typical electronic printing method, an original image is first scanned to create a digital representation of the original scene. The data obtained is usually electronically enhanced to achieve desired effects such as increased image sharpness, reduced graininess and color correction. The exposure data is then provided to an electronic printer which reconstructs the data into a photographic print by means of small discrete elements (pixels) that together constitute an image. In a conventional electronic printing method, the recording element is scanned by one or more high energy beams to provide a short duration exposure in a pixel-by-pixel mode using a suitable source, such as a light emitting diode (LED) or laser. A cathode ray tube (CRT) is also sometimes used as a printer light source in some devices. Such methods are described in the patent literature, including, for example, Hioki U.S. Pat. No. 5,126,235; European Patent Application 479 167 A1 and European Patent Application 502 508 A1. Also, many of the basic principles of electronic printing are provided in Hunt, The Reproduction of Colour, Fourth Edition, pages 306-307, (1987). Budz et al U.S. Pat. No. 5,451,490 discloses an improved electronic printing method which comprises subjecting a radiation sensitive silver halide emulsion layer of a recording element to actinic radiation of at least 10⁻⁴ ergs/cm² for up to 100μ seconds duration in a pixel-by-pixel mode. The radiation sensitive silver halide emulsion layer contains a silver halide grain population comprising at least 50 mole percent chloride, based on silver, forming the grain population projected area. At least 50 percent of the grain population projected area is accounted for by tabular grains that are bounded by {100} major faces having adjacent edge ratios of less than 10, each having an aspect ratio of at least 2. The substitution of a high chloride tabular grain emulsion for a high chloride cubic grain emulsion was demonstrated to reduce high intensity reciprocity failure (HIRF).

[0025] Electronic digital printing onto silver halide media frequently is subject to the appearance of various digital printing artifacts. Image artifacts which may be associated with optical scan printing on silver halide media include “digital fringing”, “contouring”, and “banding”. Of the artifacts associated with printing digital images onto silver halide media, “digital fringing”, or the formation of visually soft edges, especially around text, probably elicits the greatest objections. This artifact pertains to unwanted density formed in an area of a digital print as a result of a scanning exposure in a different area of the print. Digital fringing may be detected in pixels many lines away from area(s) of higher exposure, creating an underlying minimum density or Dmin that reduces sharpness and degrades color reproduction. “Contouring” refers to the formation of discrete density steps in highlight regions where the gradations should appear continuous. Bit limited system modulators (those that use >=210 bits, or 1024 DAC levels, designated 10 bit), e.g., may have too few levels to calibrate for density differences that are below the detection threshold of the human eye. A single bit change in exposure may, therefore, produce a density change large enough to see as a step, or contour. “Banding” is the appearance of lines, or bands, having a lower frequency than the individual raster lines, but which are parallel to the line scan direction. The bands arise from non-uniformity in the overlap exposure between scans (e.g., from mechanical vibrations) causing fluctuations in exposure in the overlap areas large enough to produce a visually detectable difference in density.

[0026] One of the most important parameters describing suitability of color paper for digital exposure is “dynamic range”, which may be defined as the amount of energy that has to be delivered to an emulsion to reach the desired printing density. For most digital printing devices the dynamic range should be equal to about 1 logE. Too wide dynamic range may result in the appearance of digital fringing in a color paper. The minimum exposure at which digital fringing becomes visually objectionable varies by digital printing device and emulsion photographic properties. Because fringing increases with exposure, the useful density range for typical commercial color photographic papers printed by scanning laser or LED (light emitting diode) exposures must be restricted to 2.2 or below, less than the full density range of the papers. Fine line images require even lower print densities due to the acute sensitivity of the eye to softening of high contrast edges.

[0027] Proper design of the paper's D-log E “characteristic curve” (see, e.g., T. H. James, The Theory of the Photographic Process, 4^(th) Ed., Macmillan, 1977, Pp. 501-504) can help minimize the occurrence of digital artifacts. In order to reduce digital fringing, e.g., a relatively high contrast is desired to enable a desired dynamic range. A relatively soft toe is also desired in the characteristic curve, however, to reduce the occurrence of banding and contouring. Lower contrast toe regions of the paper characteristic curves can alleviate contouring in a 10 bit system, e.g., as taught by Kawai, Kokai JP 05/142712-A, but the low contrast also lowers the density threshold for digital fringing.

[0028] The use of dopants in silver halide grains to modify photographic performance is well know in the photographic art, as generally illustrated, e.g., by Research Disclosure, Item 38957, I. Emulsion grains and their preparation, D. Grain modifying conditions and adjustments, paragraphs (3)-(5). Photographic performance attributes known to be affected by dopants include sensitivity, reciprocity failure, and contrast. The features of high contrast in the shoulder area and relatively soft toe contrast desired for digital printing can be obtained for color paper photographic emulsions through selection of appropriate contrast and speed enhancing dopants.

[0029] Using empirical techniques the art has over the years identified many dopants capable of increasing photographic speed. Keevert et al U.S. Pat. No. 4,945,035, e.g., was the first to teach the incorporation of a hexacoordination complex containing a transition metal and cyano ligands as a dopant in high chloride grains to provide increased sensitivity. Scientific investigations have gradually established that one general class of such speed increasing dopants share the capability of providing shallow electron trapping sites. Olm et al U.S. Pat. No. 5,503,970 and Daubendiek et al U.S. Pat. Nos. 5,494,789 and 5,503,971, here incorporated by reference, as well as Research Disclosure, Vol. 367, November 1994, Item 36736, were the first to set out comprehensive criteria for a dopant to have the capability of providing shallow electron trapping sites.

[0030] Doping with iridium is commonly performed to reduce reciprocity law failure in silver halide emulsions. According to the photographic law of reciprocity, a photographic element should produce the same image with the same exposure, even though exposure intensity and time are varied. For example, an exposure for 1 second at a selected intensity should produce exactly the same result as an exposure of 2 seconds at half the selected intensity. When photographic performance is noted to diverge from the reciprocity law, this is known as reciprocity failure. Specific iridium dopants proposed for use in high chloride emulsions include hexachloride complexes such as those illustrated by Bell U.S. Pat. Nos. 5,474,888, 5,480,771 and 5,500,335 and McIntyre et al 5,597,686. Specific combinations of iridium and other metal dopants may additionally be found in U.S. Pat. Nos. 4,828,962, 5,153,110, 5,219,722, 5,227,286, and 5,229,263, and European Patent Applications EP 0 244 184, EP 0 405 938, EP 0 476 602, EP 0 488 601, EP 0 488 737, EP 0 513 748, and EP 0 514 675.

[0031] The contrast of photographic elements containing silver halide emulsions can generally be increased by incorporating into the silver halide grains a dopant capable of creating deep electron trapping sites, such as illustrated by R. S. Eachus, R. E. Graves and M. T. Olm J. Chem. Phys., Vol. 69, pp. 4580-7 (1978) and Physica Status Solidi A, Vol. 57, 429-37 (1980) and R. S. Eachus and M. T. Olm Annu. Rep. Prog. Chem. Sect. C. Phys. Chem., Vol. 83, 3, pp. 3-48 (1986). U.S. Pat. Nos. 5,783,373 and 5,783,378 discuss use of combinations of transition metal complex dopants containing a nitrosyl or thionitrosyl ligand with shallow electron trapping dopants (and further with iridium coordination complex dopants for reciprocity performance) for high chloride emulsions in order to provide increased contrast in a photographic print material specifically for use in digital imaging. The use of dopant coordination complexes containing organic ligands is disclosed by Olm et al U.S. Pat. No. 5,360,712, Olm et al U.S. Pat. No. 5,457,021 and Kuromoto et al U.S. Pat. No. 5,462,849.

[0032] It has become increasing clear that with the continuing development of a variety of high intensity digital printing devices that photographic print materials with performance invariant to exposure time is increasingly important. When exposure times are reduced below one second to very short intervals (e.g., 10⁻⁵ second or less), higher exposure intensities must be employed to compensate for the reduced exposure times. High intensity reciprocity failure (hereinafter also referred to as HIRF) occurs when photographic performance is noted to depart from the reciprocity law when such shorter exposure times are employed. Print materials which traditionally suffer speed or contrast losses at short exposure times (high intensity exposures) will fail to reproduce detail with high resolution. Text will appear blurred. Through-put of digital print devices will suffer as well. Accordingly, print materials with reduced HIRF are desired in order to produce excellent photographic prints in a wide variety of digital printers. In addition to reducing HIRF, it is also desirable to reduce low intensity reciprocity failure (LIRF) in photographic elements. Print materials with reduced LIRF, e.g., will allow enlargements of photographs to be made by conventional optical printing techniques with a more faithful matching of image tone and color.

[0033] Accordingly, a current challenge in the manufacture of photographic materials, and in particular color photographic print materials such as photographic color paper, is to develop silver halide emulsions which achieve reduced reciprocity at both high and low intensity exposures. High intensity reciprocity can be obtained through the use of iridium dopants as discussed above. However, this has generally required the use of relatively high levels of iridium doping which may lead to latent image keeping problems as well as speed and contrast loss.

[0034] U.S. Pat. No. 6,107,018 discloses that a combination of shallow electron trapping dopants and iridium dopants in high chloride emulsion grains provides greater reduction in reciprocity law failure than can be achieved with either dopant alone, particularly for high intensity and short duration exposures, enabling high intensity reciprocity with iridium at relatively low levels. In all examples therein, while the shallow electron dopant and the iridium dopant are both introduced into a central portion of the silver chloride emulsion grains, they are incorporated in distinct, separate dopant bands.

[0035] U.S. Pat. No. 5,783,373 discloses possible ranges for incorporation of shallow electron trapping dopants and iridium dopants in high chloride emulsion grains which overlap, but there is no teaching or disclosure of the use of such dopants in a common dopant band. In every example where the dopants are employed in the same emulsion grains, they are present in separate bands.

[0036] U.S. Pat. No. 5,474,888 discloses a silver halide photographic material comprising cubic high chloride emulsions that have been doped using a combination of shallow electron trapping and iridium dopants. A wide variety of possible dopant locations are described, and the only examples which employ such dopants in a common band employ an iron complex dopant in combination with a low level of iridium dopant at a location relatively close to the grain surface (93-95% precipitation band).

[0037] It would be desirable to further improve upon the reciprocity performance achieved by emulsions doped in accordance with the teachings of the prior art, such as, e.g., demonstrated in U.S. Pat. Nos. 5,474,888, 5,783,373, and 6,107,018, while also improving speed and contrast sensitometric properties.

SUMMARY OF THE INVENTION

[0038] In one aspect this invention is directed towards a radiation-sensitive emulsion comprised of silver halide grains (a) containing greater than 50 mole percent chloride, based on silver, (b) having greater than 50 percent of their surface area provided by {100} crystal faces, and (c) having a central portion accounting for up to 99 percent of total silver and containing a first dopant of Formula (1):

[RuL₆]^(n)  (I)

[0039] wherein n is −2, −3 or −4, and L₆ represents bridging ligands which can be independently selected, provided that at least four of the ligands are anionic ligands, and at least one of the ligands is a cyano ligand or a ligand more electronegative than a cyano ligand; and

[0040] a second dopant comprising an iridium coordination complex having ligands each of which are more electropositive than a cyano ligand;

[0041] wherein the first dopant and the second dopants are located together in a common dopant band in an interior shell region of the central portion of the silver halide grains that surrounds at least 70 percent of the silver and, with the more centrally located silver, accounts for 90 percent of the silver halide forming the grains, and wherein the second dopant is present in the silver halide grains in a concentration of at least 10⁻⁷ mole/mole of total silver.

[0042] In a second aspect, this invention is directed towards a photographic recording element comprising a support and at least one light sensitive silver halide emulsion layer comprising silver halide grains as described above.

[0043] In another aspect, this invention is directed to an electronic printing method which comprises subjecting a radiation sensitive silver halide emulsion layer of a recording element to actinic radiation of at least 10⁻⁴ ergs/cm² for up to 100μ seconds duration in a pixel-by-pixel mode, wherein the silver halide emulsion layer is comprised of silver halide grains as described above.

[0044] It has been discovered quite surprisingly that the combination of first and second dopants in a common dopant band provides greater reduction in reciprocity law failure than is achieved with such dopants in separate bands. The combination of dopants further unexpectedly achieves high intensity reciprocity with iridium at relatively lower levels, and also provides improvements in speed and contrast properties. In a preferred practical application, the advantages of the invention can be transformed into increased throughput of digital artifact-free color print images while exposing each pixel sequentially in synchronism with the digital data from an image processor.

DESCRIPTION OF PREFERRED EMBODIMENTS

[0045] In one embodiment, the present invention represents an improvement on the electronic printing method disclosed by Budz et al, cited above and here incorporated by reference. Specifically, this invention in one embodiment is directed to an electronic printing method which comprises subjecting a radiation sensitive silver halide emulsion layer of a recording element to actinic radiation of at least 10⁻⁴ ergs/cm² for up to 100μ seconds duration in a pixel-by-pixel mode. The present invention realizes an improvement in latent image keeping by modifying the radiation sensitive silver halide emulsion layer. While certain embodiments of the invention are specifically directed towards electronic printing, use of the emulsions and elements of the invention is not limited to such specific embodiment, and it is specifically contemplated that the emulsions and elements of the invention are also well suited for conventional optical printing.

[0046] Emulsions in accordance with the invention comprise high chloride silver halide grains, which include a doped inner portion including a shallow electron trapping hexacoordination complex dopant of Formula (I):

[RuL₆]^(n)  (I)

[0047] wherein n is −2, −3 or −4, and L₆ represents bridging ligands which can be independently selected, provided that at least four of the ligands are anionic ligands, and at least one (preferably at least 3 and optimally at least 4) of the ligands is a cyano ligand or a ligand more electronegative than a cyano ligand. Any remaining ligands can be selected from among various other bridging ligands, including aquo ligands, halide ligands (specifically, fluoride, chloride, bromide and iodide), cyanate ligands, thiocyanate ligands, selenocyanate ligands, tellurocyanate ligands, and azide ligands. Hexacoordinated complexes of Formula (I) which include six cyano ligands are specifically preferred.

[0048] Illustrations of specifically contemplated Formula (I) hexacoordination complexes for inclusion in the high chloride grains are provided by Bell U.S. Pat. Nos. 5,474,888, 5,470,771 and 5,500,335, Olm et al U.S. Pat. No. 5,503,970 and Daubendiek et al U.S. Pat. Nos. 5,494,789 and 5,503,971, and Keevert et al U.S. Pat. No. 4,945,035, the disclosures of which are here incorporated by reference, as well as Murakami et al Japanese Patent Application Hei-2[1990]-249588, and Research Disclosure Item 36736, the disclosures of which are here incorporated by reference. Useful neutral and anionic organic ligands for dopant hexacoordination complexes are disclosed by Olm et al U.S. Pat. No. 5,360,712 and Kuromoto et al U.S. Pat. No. 5,462,849, the disclosures of which are here incorporated by reference.

[0049] The following are specific illustrations of Formula (1) dopants:

[RuCO(CN)₅]⁻³  (I-1)

[Ru(CN)₆]⁻⁴  (I-2)

[RuCl(CN)₅]⁻⁴  (I-3)

[RuF₂(CN)₄]⁻⁴  (I-4)

[Ru(CN)₅(OCN)]⁻⁴  (I-5)

[Ru(CN)₅(N₃)]⁻⁴  (I-6)

[RU(CO)₂(CN)₄]⁻²  (I-7)

[0050] The Formula (I) dopants have a net negative charge, it is appreciated that they are associated with a counter ion when added to the reaction vessel during precipitation. The counter ion is of little importance, since it is ionically dissociated from the dopant in solution and is not incorporated within the grain. Common counter ions known to be fully compatible with silver chloride precipitation, such as ammonium and alkali metal ions, are contemplated. It is noted that the same comments apply to iridium dopants also employed in accordance with the invention, otherwise described below.

[0051] The second dopant located together with the first dopant in a common dopant band within the central portion of the silver halide grains in accordance with the invention comprising an iridium coordination complex having ligands each of which are more electropositive than a cyano ligand. Preferably, at least one ligand of the iridium complex dopant comprises a thiazole or substituted thiazole ligand. The thiazole ligands may be substituted with any photographically acceptable substituent which does not prevent incorporation of the dopant into the silver halide grain. Exemplary substituents include lower alkyl (e.g., alkyl groups containing 1-4 carbon atoms), and specifically methyl. A specific example of a substituted thiazole ligand which may be used in accordance with preferred embodiments of the invention is 5-methylthiazole. In a specifically preferred form the remaining non-thiazole or non-substituted-thiazole ligands of the second dopant iridium coordination complexes are halide ligands.

[0052] It is specifically contemplated to select the second dopant from among the iridium coordination complexes containing organic ligands disclosed by Olm et al U.S. Pat. No. 5,360,712, Olm et al U.S. Pat. No. 5,457,021 and Kuromoto et al U.S. Pat. No. 5,462,849, the disclosures of which are here incorporated by reference.

[0053] In a preferred form it is contemplated to employ as the second dopant a hexacoordination complex satisfying the formula:

[IrL¹ ₆]^(n′)  (II)

[0054] wherein

[0055] n′ is zero, −1, −2, −3 or −4; and

[0056] L¹ ₆ represents six bridging ligands which can be independently selected, provided that at least four of the ligands are anionic ligands, each of the ligands is more electropositive than a cyano ligand, and at least one of the ligands comprises a thiazole or substituted thiazole ligand. In a specifically preferred form at least four of the ligands are halide ligands, such as chloride or bromide ligands.

[0057] Specific illustrations of Formula (II) dopants are the following:

[IrCl₅(thiazole)]⁻²  (II-1)

[IrCl₄(thiazole)₂]⁻¹  (II-2)

[IrBr₅(thiazole)]⁻²  (II-3)

[IrBr₄(thiazole)₂]⁻¹  (II-4)

[IrCl₅(5-methylthiazole)]⁻²  (II-5)

[IrCl₄(5-methylthiazole)₂]⁻¹  (II-6)

[IrBr₅(5-methylthiazole)]⁻²  (II-7)

[IrBr₄(5-methylthiazole)₂]⁻¹  (II-8)

[0058] In accordance with the invention, the first dopant of Formula (I) and the second dopant comprising an iridium complex are contained in a common dopant band within the central portion of the high chloride emulsion grains. Emulsions demonstrating the advantages of the invention can be realized by modifying the precipitation of conventional high chloride silver halide grains having predominantly (>50%) {100} crystal faces to obtain grains incorporating the above described first and second dopants as described above within a common dopant band. To be located within a common dopant band, both dopants should be introduced concurrently (either by separate jets or by a common jet) into a silver halide reaction vessel during precipitation of at least a part of the central portion of the emulsion grains. The dopants are introduced into the high chloride grains after at least 70 (most preferably 75) percent of the silver has been precipitated for such grains, but before 90 percent of the silver has been precipitated. Stated in terms of the fully precipitated grain structure, the first dopant of Formula (I) and the second dopant comprising an iridium complex are present together in an interior shell region that surrounds at least 70 (preferably 75) percent of the silver and, with the more centrally located silver, for 90 percent of the silver halide forming the high chloride grains.

[0059] The Formula (I) and iridium coordination complex dopants can be employed in any useful concentrations. The silver halide grains preferably contain from 10⁻⁸ to 10⁻³ mole (more preferably from 10⁻⁷ to 10⁻⁴ mole) of a dopant of Formula (I), and from 10⁻⁷ to 10⁻⁴ mole (more preferably from 10⁻⁷ to 10⁻⁵ mole) of an iridium coordination complex dopant per total mole of silver.

[0060] The performance improvements described in accordance with the invention may be obtained for silver halide grains employing conventional gelatino-peptizer, as well as oxidized gelatin (e.g., gelatin having less than 30 micromoles of methionine per gram). Accordingly, in specific embodiments of the invention, it is specifically contemplated to use significant levels (i.e., greater than 1 weight percent of total peptizer) of conventional gelatin (e.g., gelatin having at least 30 micromoles of methionine per gram) as a gelatino-peptizer for the silver halide grains of the emulsions of the invention. In preferred embodiments of the invention, gelatino-peptizer is employed which comprises at least 50 weight percent of gelatin containing at least 30 micromoles of methionine per gram, as it is frequently desirable to limit the level of oxidized low methionine gelatin which may be used for cost and certain performance reasons.

[0061] The silver halide grains precipitated contain greater than 50 mole percent chloride, based on silver. Preferably the grains contain at least 70 mole percent chloride and, optimally at least 90 mole percent chloride, based on silver. Iodide can be present in the grains up to its solubility limit, which is in silver iodochloride grains, under typical conditions of precipitation, about 11 mole percent, based on silver. It is preferred for most photographic applications to limit iodide to less than 5 mole percent iodide, most preferably less than 2 mole percent iodide, based on silver.

[0062] Silver bromide and silver chloride are miscible in all proportions. Hence, any portion, up to 50 mole percent, of the total halide not accounted for chloride and iodide, can be bromide. For color reflection print (i.e., color paper) uses bromide is typically limited to less than 10 mole percent based on silver and iodide is limited to less than 1 mole percent based on silver.

[0063] The silver halide grains of photographic emulsions in accordance with the invention may also include other dopants, such as nitrosyl or thionitrosyl ligand containing dopants as disclosed in U.S. Pat. Nos. 4,933,272, 5,783,373 and 5,783,378, the disclosures of which are here incorporated by reference.

[0064] In a widely used form high chloride grains are precipitated to form cubic grains, that is, grains having {100} major faces and edges of equal length. In practice ripening effects usually round the edges and corners of the grains to some extent. However, except under extreme ripening conditions substantially more than 50 percent of total grain surface area is accounted for by {100} crystal faces.

[0065] High chloride tetradecahedral grains are a common variant of cubic grains. These grains contain 6 {100} crystal faces and 8 {111} crystal faces. Tetradecahedral grains are within the contemplation of this invention to the extent that greater than 50 percent of total surface area is accounted for by {100} crystal faces.

[0066] Although it is common practice to avoid or minimize the incorporation of iodide into high chloride grains employed in color paper, it is has been recently observed that silver iodochloride grains with {100} crystal faces and, in some instances, one or more {111} faces offer exceptional levels of photographic speed. In the these emulsions iodide is incorporated in overall concentrations of from 0.05 to 3.0 mole percent, based on silver, with the grains having a surface shell of greater than 50 Å that is substantially free of iodide and a interior shell having a maximum iodide concentration that surrounds a core accounting for at least 50 percent of total silver. Such grain structures are illustrated by Chen et al EPO 0 718 679.

[0067] In another improved form the high chloride grains can take the form of tabular grains having {100} major faces. Preferred high chloride {100} tabular grain emulsions are those in which the tabular grains account for at least 70 (most preferably at least 90) percent of total grain projected area. Preferred high chloride {100} tabular grain emulsions have average aspect ratios of at least 5 (most preferably at least >8). Tabular grains typically have thicknesses of less than 0.3 μm, preferably less than 0.2 μm, and optimally less than 0.07 μm. High chloride {100} tabular grain emulsions and their preparation are disclosed by Maskasky U.S. Pat. Nos. 5,264,337 and 5,292,632, House et al U.S. Pat. No. 5,320,938, Brust et al U.S. Pat. No. 5,314,798 and Chang et al U.S. Pat. No. 5,413,904, the disclosures of which are here incorporated by reference.

[0068] Once high chloride grains having predominantly {100} crystal faces have been precipitated doped with a combination of dopants as described above, chemical and spectral sensitization, followed by the addition of conventional addenda to adapt the emulsion for the imaging application of choice can take any convenient conventional form. The conventional features are further illustrated by Research Disclosure, Item 38957, cited above, particularly:

[0069] III. Emulsion washing;

[0070] IV. Chemical sensitization;

[0071] V. Spectral sensitization and desensitization;

[0072] VII. Antifoggants and stabilizers;

[0073] VIII. Absorbing and scattering materials;

[0074] IX. Coating and physical property modifying addenda; and

[0075] X. Dye image formers and modifiers.

[0076] As pointed out by Bell, cited above, some additional silver halide, typically less than 1 percent, based on total silver, can be introduced to facilitate chemical sensitization. It is also recognized that silver halide can be epitaxially deposited at selected sites on a host grain to increase its sensitivity. For example, high chloride {100} tabular grains with corner epitaxy are illustrated by Maskasky U.S. Pat. No. 5,275,930. For the purpose of providing a clear demarcation, the term “silver halide grain” is herein employed to include the silver necessary to form the grain up to the point that the final {100} crystal faces of the grain are formed. Silver halide later deposited that does not overlie the {100} crystal faces previously formed accounting for at least 50 percent of the grain surface area is excluded in determining total silver forming the silver halide grains. Thus, the silver forming selected site epitaxy is not part of the silver halide grains while silver halide that deposits and provides the final {100} crystal faces of the grains is included in the total silver forming the grains, even when it differs significantly in composition from the previously precipitated silver halide.

[0077] In the simplest contemplated form a photographic element of the invention can consist of a single emulsion layer satisfying the emulsion description provided above coated on a conventional photographic support, such as those described in Research Disclosure, Item 38957, cited above, XVI. Supports. In one preferred form the support is a white reflective support, such as photographic paper support or a film support that contains or bears a coating of a reflective pigment. To permit a print image to be viewed using an illuminant placed behind the support, it is preferred to employ a white translucent support, such as a Duratrans™ or Duraclear™ support.

[0078] The photographic elements and printing methods of the invention can be used to form either silver or dye images in the recording element. In a simple form a single radiation sensitive emulsion layer unit is coated on the support. The elements can contain one or more high chloride silver halide emulsions satisfying the requirements of the invention. When a dye imaging forming compound, such as a dye-forming coupler, is present it can be in an emulsion layer or in a layer coated in contact with the emulsion layer. With a single emulsion layer unit a monochromatic image is obtained.

[0079] In a preferred embodiment the invention employs recording elements which are constructed to contain at least three silver halide emulsion layer units. A suitable multicolor, multilayer format for a recording element used in the invention is represented by Structure I. Blue-sensitized yellow dye image-forming silver halide emulsion unit Interlayer Green-sensitized magenta dye image-forming silver halide emulsion unit Interlayer Red-sensitized cyan dye image-forming silver halide emulsion unit ///// Support /////

Structure I

[0080] wherein the red-sensitized, cyan dye image-forming silver halide emulsion unit is situated nearest the support; next in order is the green-sensitized, magenta dye image-forming unit, followed by the uppermost blue-sensitized, yellow dye image-forming unit. The image-forming units are separated from each other by hydrophilic colloid interlayers containing an oxidized developing agent scavenger to prevent color contamination. Silver halide emulsions satisfying the requirements described above can be present in any one or combination of the emulsion layer units. Additional useful multicolor, multilayer formats for an element of the invention include Structures II-IV as described in U.S. Pat. No. 5,783,373 referenced above, which is incorporated by reference herein. Each of such structures in accordance with the invention would contain at least one silver halide emulsion comprised of high chloride grains having at least 50 percent of their surface area bounded by {100} crystal faces and containing dopants as described above. Preferably each of the emulsion layer units contain an emulsion satisfying these criteria.

[0081] Conventional features that can be incorporated into multilayer (and particularly multicolor) recording elements contemplated for use in the invention are illustrated by Research Disclosure, Item 38957, cited above:

[0082] XI. Layers and layer arrangements

[0083] XII. Features applicable only to color negative

[0084] XIII. Features applicable only to color positive

[0085] B. Color reversal

[0086] C. Color positives derived from color negatives

[0087] XIV. Scan facilitating features.

[0088] The recording elements comprising the radiation sensitive high chloride emulsion layers according to this invention can be conventionally optically printed, or in accordance with a particular embodiment of the invention can be image-wise exposed in a pixel-by-pixel mode using suitable high energy radiation sources typically employed in electronic printing methods. Suitable actinic forms of energy encompass the ultraviolet, visible and infrared regions of the electromagnetic spectrum as well as electron-beam radiation and is conveniently supplied by beams from one or more light emitting diodes or lasers, including gaseous or solid state lasers. Exposures can be monochromatic, orthochromatic or panchromatic. For example, when the recording element is a multilayer multicolor element, exposure can be provided by laser or light emitting diode beams of appropriate spectral radiation, for example, infrared, red, green or blue wavelengths, to which such element is sensitive. Multicolor elements can be employed which produce cyan, magenta and yellow dyes as a function of exposure in separate portions of the electromagnetic spectrum, including at least two portions of the infrared region, as disclosed in the previously mentioned U.S. Pat. No. 4,619,892, incorporated herein by reference. Suitable exposures include those up to 2000 nm, preferably up to 1500 nm. The exposing source need, of course, provide radiation in only one spectral region if the recording element is a monochrome element sensitive to only that region (color) of the electromagnetic spectrum. Suitable light emitting diodes and commercially available laser sources are described in the examples. Imagewise exposures at ambient, elevated or reduced temperatures and/or pressures can be employed within the useful response range of the recording element determined by conventional sensitometric techniques, as illustrated by T. H. James, The Theory of the Photographic Process, 4th Ed., Macmillan, 1977, Chapters 4, 6, 17, 18 and 23.

[0089] The quantity or level of high energy actinic radiation provided to the recording medium by the exposure source is generally at least 10⁻⁴ ergs/cm², typically in the range of about 10⁻⁴ ergs/cm² to 10⁻³ ergs/cm² and often from 10⁻³ ergs/cm² to 10⁻² ergs/cm². Exposure of the recording element in a pixel-by-pixel mode as known in the prior art persists for only a very short duration or time. Typical maximum exposure times are up to 100μ seconds, often up to 10μ seconds, and frequently up to only 0.5μ seconds. Single or multiple exposures of each pixel are contemplated. The pixel density is subject to wide variation, as is obvious to those skilled in the art. The higher the pixel density, the sharper the images can be, but at the expense of equipment complexity. In general, pixel densities used in conventional electronic printing methods of the type described herein do not exceed 10⁷ pixels/cm² and are typically in the range of about 10⁴ to 10⁶ pixels/cm². An assessment of the technology of high-quality, continuous-tone, color electronic printing using silver halide photographic paper which discusses various features and components of the system, including exposure source, exposure time, exposure level and pixel density and other recording element characteristics is provided in Firth et al., A Continuous-Tone Laser Color Printer, Journal of Imaging Technology, Vol. 14, No. 3, June 1988, which is hereby incorporated herein by reference. As previously indicated herein, a description of some of the details of conventional electronic printing methods comprising scanning a recording element with high energy beams such as light emitting diodes or laser beams, are set forth in Hioki U.S. Pat. No. 5,126,235, European Patent Applications 479 167 A1 and 502 508 A1, the disclosures of which are hereby incorporated herein by reference.

[0090] Once imagewise exposed, the recording elements can be processed in any convenient conventional manner to obtain a viewable image. As demonstrated in the examples below, photographic elements in accordance with the invention demonstrate improved latent image keeping performance, decreasing the impact of delays in processing which may occur after imagewise exposure. Conventional processing is illustrated, e.g., by Research Disclosure, Item 38957, cited above:

[0091] XVIII. Chemical development systems

[0092] XIX. Development

[0093] XS. Desilvering, washing, rinsing and stabilizing

EXAMPLES

[0094] This invention can be better appreciated by reference to the following Examples. Emulsions EM-1 throughout EM-10 illustrate the preparation of radiation sensitive high chloride emulsions, both for comparison and inventive emulsions employed in examples 1-3. Examples 1 through 7 illustrate that recording elements containing layers of emulsions in accordance with the invention exhibit unexpected advantageous characteristics relative to comparison emulsions that make them particularly useful in very fast optical printers and in electronic printing methods of the type described herein.

[0095] Emulsion Precipitations

[0096] Emulsion EM-1: A reaction vessel contained 6.92 L of a solution that was 3.8% in regular gelatin and contained 1.71 g of a Pluronic antifoam agent. To this stirred solution at 46° C. 83.5 mL of 3.0 M NaCl was dumped, and soon after 28.3 mL of dithiaoctanediol solution was poured into the reactor. A half minute after addition of dithiaoctanediol solution, 104.5 mL of a 2.8 M AgNO₃ solution and 107.5 mL of 3.0 M NaCl were added simultaneously at 209 mL/min for 0.5 minute. The vAg set point was chosen equal to that observed in the reactor at this time. Then the 2.8 M silver nitrate solution and the 3.0 M sodium chloride solution were added simultaneously with a constant flow at 209 mL/min over 20.75 minutes. The resulting silver chloride emulsion had a cubic shape that was 0.38 μm in edgelength. The emulsion was then washed using an ultrafiltration unit, and its final pH and pCl were adjusted to 5.6 and 1.8, respectively.

[0097] Emulsion EM-2: This emulsion was precipitated exactly as Emulsion EM-1, except that 0.25 milligrams (0.0004 mmol) per silver mole of the potassium salt of dopant II-5, K₂IrCl₅(5-methylthiazole).2H₂O, was added during to 90 to 95% of grain formation.

[0098] Emulsion EM-3: This emulsion was precipitated exactly as Emulsion EM-1, except that 16.54 milligrams (0.040 mmol) per silver mole of the potassium salt of dopant I-2, K₄Ru(CN)₆, was added during 75 to 80% of grain formation.

[0099] Emulsion EM-4: This emulsion was precipitated exactly as Emulsion EM-1, except that 16.54 milligrams per silver mole of K₄Ru(CN)₆ was added during 75 to 80% of grain formation, and 0.25 milligrams per silver mole of K₂IrCl₅(5-methylthiazole).2H₂O was added during to 90 to 95% of grain formation.

[0100] Emulsion EM-5: This emulsion was precipitated exactly as Emulsion EM-1, except that mixture of 16.54 milligrams per silver mole of K₄Ru(CN)₆ and 0.25 milligrams per silver mole of K₂IrCl₅(5-methylthiazole).2H₂O and was added during 75 to 80% of grain formation.

[0101] Emulsion EM-6: This emulsion was precipitated exactly as Emulsion EM-5, except that K₄Ru(CN)₆ and K₂IrCl₅(5-methylthiazole).2H₂O solutions were added using separate jets.

[0102] Emulsion EM-7: This emulsion was precipitated exactly as Emulsion EM-1, except that 0.087 milligrams (0.00014 mmol) per silver mole of K₂IrCl₅(5-methylthiazole).2H₂O was added during to 90 to 95% of grain formation.

[0103] Emulsion EM-8: This emulsion was precipitated exactly as Emulsion EM-1, except that 4.1 milligrams (0.0099 mmol) per silver mole of K₄Ru(CN)₆ was added during 75 to 80% of grain formation.

[0104] Emulsion EM-9: This emulsion was precipitated exactly as Emulsion EM-1, except that 4.1 milligrams per silver mole of K₄Ru(CN)₆ was added during 75 to 80% of grain formation, and 0.087 milligrams per silver mole of K₂IrCl₅(5-methylthiazole).2H₂O was added during to 90 to 95% of grain formation.

[0105] Emulsion EM-10: This emulsion was precipitated exactly as Emulsion EM-1, except that mixture of 4.1 milligrams per silver mole of K₄Ru(CN)₆ and 0.087 milligrams per silver mole of K₂IrCl₅(5-methylthiazole).2H₂O and was added during 75 to 80% of grain formation.

Sensitization of Emulsions

[0106] The emulsions were each optimally sensitized by the customary techniques using two basic sensitization schemes. The sequence of chemical sensitizers, spectral sensitizers, and antifoggants addition are the same for each finished emulsion. Both colloidal gold sulfide or gold(I) (as disclosed in U.S. Pat. No. 5, 945,270) and hypo (Na₂S₂O₃) were used for chemical sensitization. Detailed procedures are described in the Examples below.

[0107] In red-sensitized emulsions the following red spectral sensitizing dye was used:

[0108] Spectral Sensitizing Dye A

[0109] Just prior to coating on resin coated paper support red-sensitized emulsions were dual-mixed with cyan dye forming coupler A:

Coupler A:

[0110]

[0111] In green-sensitized emulsions the following green spectral sensitizing dye was used:

Spectral Sensitizing Dye B:

[0112]

[0113] Just prior to coating on resin coated paper support green-sensitized emulsions were dual-mixed with magenta dye forming coupler B:

Coupler B:

[0114]

[0115] In blue-sensitized emulsions the following blue spectral sensitizing dye was used:

Spectral Sensitizing Dye C:

[0116]

[0117] Just prior to coating on resin coated paper support blue-sensitized emulsions were dual-mixed with yellow dye forming coupler C:

Coupler C:

[0118]

[0119] The red-sensitized emulsions were coated at 194 mg silver per square meter, green-sensitized emulsions were coated at 108 mg silver per square meter, and blue-sensitized emulsions were coated at 280 mg silver per square meter on resin-coated paper support. The coatings were overcoated with gelatin layer and the entire coating was hardened with bis(vinylsulfonylmethyl)ether.

Photographic Comparisons

[0120] Coatings were exposed through a step wedge with 3000 K tungsten source at high-intensity short exposure (10⁻² to ₁₀ ⁻⁴ second for red and blue sensitized emulsions and 10⁻³ to 10⁻⁵ second for green sensitized emulsions) or low-intensity, long exposure times (10 to 0.1 second for red and blue sensitized emulsions and 1 to 10⁻² second for green sensitized emulsions). The total energy of each exposure was kept at a constant level. Speed is reported as relative log speed (RLS) at specified level above the minimum density as presented in the following Examples. In relative log speed units a speed difference of 30, for example, is a difference of 0.30 log E, where E is exposure in lux-seconds. These exposures will be referred to as “Optical Sensitivity” in the following Examples.

[0121] Coatings were also exposed with three color laser sensitometer exposure apparatus at 691 nm (red sensitized emulsions), 532 nm (green sensitized emulsions) or 470 nm (blue sensitized emulsions), a resolution of 98.4 pixels/cm, a pixel pitch of 100 μm, and the exposure time of 1 microsecond per pixel. These exposures will be referred to as “Laser Sensitivity” in the following Examples.

[0122] All coatings were processed in Kodak™ Ektacolor RA-4. Relative optical speeds were reported at Dmin+1.35 or Dmin+1.90 density levels. Relative laser speeds were reported at density level equal to 2.2. Laser contrast was measured between TOE and SHOULDER, where TOE is defined as density at density level equal 0.80 minus 0.2logE, while SHOULDER is defined as the density at density level equal to 0.80 plus 0.4logE.

Example 1

[0123] This example compares effects of K₄Ru(CN)₆ and K₂IrCl₅(5-methylthiazole).2H₂O synergy on shoulder reciprocity failure. In each case, silver chloride cubic emulsions sensitized for red color record were used. The sensitization details are as follows:

[0124] Part 1.1: A portion of silver chloride Emulsion EM-1 was optimally sensitized by the addition of p-glutaramidophenyl disulfide (GDPD) followed by addition of the optimum amount of hypo followed by addition of gold (I). The emulsion was then heated to 65° C. and held at this temperature for 30 minutes with subsequent addition of 1-(3-acetamidophenyl)-5-mercaptotetrazole followed by addition of bromide. Then the emulsion was cooled to 40° C. and Spectral Sensitizing dye A was added.

[0125] Part 1.2: A portion of silver chloride Emulsion EM-2 was sensitized exactly as in Part 1.1.

[0126] Part 1.3: A portion of silver chloride Emulsion EM-3 was sensitized exactly as in Part 1.1.

[0127] Part 1.4: A portion of silver chloride Emulsion EM-4 was sensitized exactly as in Part 1.1.

[0128] Part 1.5: A portion of silver chloride Emulsion EM-5 was sensitized exactly as in Part 1.1.

[0129] Part 1.6: A portion of silver chloride Emulsion EM-6 was sensitized exactly as in Part 1.1.

[0130] Densitometry Data are Summarized in Table I. TABLE I Optical sensitivity HIRF LIRF Dopant Location 10⁻² s-10⁻⁴ s 10 s-0.1 s Laser Sensitivity K₂IrCl₅(5- D_(min) + D_(min) + D_(min) + D_(min) + Speed@ Part # K₄Ru(CN)₆ Methyl-Tz) 1.35 1.95 1.35 1.95 D = 2.2 Contrast 1.1 N/A N/A — — 3 7 9.0 1.316 1.2 N/A 90-95 — — 7 12 18.0 1.286 1.3 75-80 N/A — — −16.3 −12.7 12.0 1.318 1.4 75-80 90-95 10.3 29.0 −6.9 −5.8 44.0 1.933 1.5 75-80 75-80 −2.5 −1.6 −6.0 −5.0 85.0 2.324 (INV) 1.6 75-80 75-80 −2.8 −1.5 −5.9 −5.2 82.0 2.332 (INV)

[0131] It evident from Table I above that incorporation of a dopant of Formula (I) and an iridium dopant in a common dopant band in a AgCl grain sensitized for cyan record improves HIRF, laser and optical sensitometric performance over a case where the dopants are added separately at different locations within a grain. It is also evident from Table I that blending of the dopants prior to addition or adding individually at the same location results in a very similar optical and digital response of silver chloride emulsion sensitized for cyan record.

Example 2

[0132] This example compares effects of K₄Ru(CN)₆ and K₂IrCl₅(5-methylthiazole).2H₂O synergy on shoulder reciprocity failure. In each case, silver chloride cubic emulsions sensitized for yellow color record were used. The sensitization details are as follows:

[0133] Part 2.1: A portion of silver chloride Emulsion EM-I was optimally sensitized by the addition of p-glutaramidophenyl disulfide (GDPD) followed by addition of the optimum amount of gold sulfide. The emulsion was then heated to 59° C. and held at this temperature for 18 minutes with subsequent addition of Spectral Sensitizing Dye C followed by addition of Lippmann bromide and followed by addition of 1-(3-acetamidophenyl)-5-mercaptotetrazole. Then the emulsion was cooled to 40° C. and sodium chloride was added.

[0134] Part 2.2: A portion of silver chloride Emulsion EM-7 was sensitized exactly as in Part 2.1.

[0135] Part 2.3: A portion of silver chloride Emulsion EM-8 was sensitized exactly as in Part 2.1.

[0136] Part 2.4: A portion of silver chloride Emulsion EM-9 was sensitized exactly as in Part 2.1. Part 2.5: A portion of silver chloride Emulsion EM-10 was sensitized exactly as in Part 2.1.

[0137] Densitometry Data are Summarized in Table II. TABLE II Optical sensitivity HIRF LIRF Dopant Location 10⁻² s-10⁻⁴ s 10 s-0.1 s Laser Sensitivity K₂IrCl₅(5- D_(min) + D_(min) + D_(min) + D_(min) + Speed@ Part # K₄Ru(CN)₆ Methyl-Tz) 1.35 2.20 1.35 2.20 D = 2.2 Contrast 2.1 N/A N/A 20.9 41.1 −22.5 −24.8 3 1.521 2.2 N/A 90-95 −3.9 0.6 −9.2 −13.2 19 1.686 2.3 75-80 N/A 21.2 41.3 −26.1 −36.5 10 1.647 2.4 75-80 90-95 −3.1 −2.8 −7.4 −15.9 34 2.295 2.5 75-80 75-80 −3.0 −1.6 −2.1 −7.4 49 2.435 (INV)

[0138] It evident from Table II above that incorporation of a dopant of Formula (I) and an iridium dopant in a common dopant band in a AgCl grain sensitized for yellow record improves HIRF, laser and optical sensitometric performance over a case where the dopants are added separately at different locations within a grain.

Example 3

[0139] This example compares effects of K₄Ru(CN)₆ and K₂IrCl₅(5-methylthiazole).2H₂O synergy on shoulder reciprocity failure. In each case, silver chloride cubic emulsions sensitized for the magenta color record were used. The sensitization details are as follows:

[0140] Part 3.1: A portion of silver chloride Emulsion EM-1 was optimally sensitized by the addition of p-glutaramidophenyl disulfide (GDPD) followed by addition of the optimum amount of gold sulfide. The emulsion was then heated to 55° C. and held at this temperature for 35 minutes with subsequent addition of Spectral Sensitizing Dye B followed by addition of Lippmann bromide and followed by addition of 1-(3-acetamidophenyl)-5-mercaptotetrazole. Then the emulsion was cooled to 40° C. and sodium chloride was added.

[0141] Part 3.2: A portion of silver chloride Emulsion EM-7 was sensitized exactly as in Part 3.1.

[0142] Part 3.3: A portion of silver chloride Emulsion EM-8 was sensitized exactly as in Part 3.1.

[0143] Part 3.4: A portion of silver chloride Emulsion EM-9 was sensitized exactly as in Part 3.1.

[0144] Part 3.5: A portion of silver chloride Emulsion EM-10 was sensitized exactly as in Part 3.1.

[0145] Part 3.6: A portion of silver chloride Emulsion EM-11 was sensitized exactly as in Part 3.1.

[0146] Densitometry Data are Summarized in Table III. TABLE III Optical sensitivity HIRF LIRF Dopant Location 10⁻³ s-10⁻⁵ s 1 s-0.01 s Laser Sensitivity K₂IrCl₅(5- D_(min) + D_(min) + D_(min) + D_(min) + Speed@ Part # K₄Ru(CN)₆ Methyl-Tz) 1.35 1.95 1.35 1.95 D = 2.2 Contrast 3.1 N/A N/A 39.3 — 24.5 18.1 37.3 1.480 3.2 N/A 90-95 5.9 26.7 11.3 14.5 25.5 1.889 3.3 75-80 N/A 31.4 — 19.7 11.7 43.5 1.475 3.4 75-80 90-95 3.4 10.8 4.2 5.5 67.1 1.790 3.5 75-80 75-80 1.2 1.3 −1.8 −2.1 79.1 2.220 (INV) 3.6 75-80 75-80 2.3 7.5 −1.0 5.2 88.1 2.309 (INV)

[0147] It evident from Table III above that incorporation of a dopant of Formula (I) and an iridium dopant in a common dopant band in a AgCl grain sensitized for magenta record improves HIRF, laser and optical sensitometric performance over a case where the dopants are added separately at different locations within a grain.

Example 4

[0148] This example compares effects of K₄Ru(CN)₆ and K₂IrCl₅(5-methylthiazole).2H₂O synergy on shoulder reciprocity failure. Emulsions for Parts 4.1 and 4.2 were precipitated similarly as for Emulsion EM-1, except that 16.54 milligrams (0.040 mmol) per silver mole of K₄Ru(CN)₆ and 0.25 milligrams (0.0004 mmol) per silver mole of K₂IrCl₅(5-methylthiazole).2H₂O were added during grain formation as indicated in Table IV.

[0149] In each case, silver chloride cubic emulsions sensitized similarly as for Part 1.1 for the red color record were used. TABLE IV Optical sensitivity HIRF LIRF Dopant Location 10⁻² s-10⁻⁴ s 10 s-0.1 s Laser Sensitivity K₂IrCl₅(5- D_(min) + D_(min) + D_(min) + D_(min) + Speed@ Part # K₄Ru(CN)₆ Methyl-Tz) 1.35 1.95 1.35 1.95 D = 2.2 Contrast 4.1 50-99 93-95 48.6 44.9+ −0.1 0.9 162 2.228 4.2 75-80 75-80 3.2 5.4 −0.4 −0.6 226 2.632 (INV)

[0150] It evident from Table IV above that incorporation of a dopant of Formula (I) and an iridium dopant in a common dopant band located between 70-90% of grain precipitation in a AgCl grain record improves HIRF, laser and optical sensitometric performance over a case where the dopants are added at locations within a grain including a common band outside of 70-90% of grain formation.

Example 5

[0151] This example compares effects of K₄Ru(CN)₆ and K₂IrCl₅(5-methylthiazole).2H₂O synergy on shoulder reciprocity failure. Emulsions for Parts 4.1-4.3 were precipitated similarly as for Emulsion EM-1, except that 16.54 milligrams (0.040 mmol) per silver mole of K₄Ru(CN)₆ and 0.25 milligrams (0.0004 mmol) per silver mole of K₂IrCl₅(5-methylthiazole).2H₂O were added during grain formation as indicated in Table V. In each case, silver chloride cubic emulsions sensitized similarly as for Part 1.1 for the red color record were used. TABLE V Optical sensitivity HIRF LIRF Dopant Location 10⁻² s-10⁻⁴ s 10 s-0.1 s Laser Sensitivity K₂IrCl₅(5- D_(min) + D_(min) + D_(min) + D_(min) + Speed@ Part # K₄Ru(CN)₆ Methyl-Tz) 1.35 1.95 1.35 1.95 D = 2.2 Contrast 5.1 75-80 75-80 −2.5 −1.6 −6.7 −5.0 85 2.670 (INV) 5.2 80-85 80-85 0.9 1.1 −5.5 −3.9 73 2.323 (INV) 5.3 90-95 90-95 10.4 28.6 −7.4 −4.3 43 1.791

[0152] It evident from Table V above that incorporation of a dopant of Formula (I) and an iridium dopant in a common dopant band located between 70-90% of grain precipitation in a AgCl grain record improves HIRF, laser and optical sensitometric performance over a case where the dopants are added in a common band outside of 70-90% of grain formation.

Example 6

[0153] This example compares effects of combinations of formula I dopant K₄Ru(CN)₆ and iridium dopant K₃IrCl₆ on shoulder reciprocity failure in comparison to the use of a combination of K₄Fe(CN)₆ and K₃IrCl₆. Emulsions for Parts 6.1-6.8 were precipitated similarly as for Emulsion EM-1, except that K₃IrCl₆ and either K₄Ru(CN)₆ or K₄Fe(CN)₆ were added during grain formation in amounts and at locations as indicated in Table VI. In each case, silver chloride cubic emulsions sensitized similarly as for Part 1.1 for the red color record were used. TABLE VI Optical sensitivity HIRF LIRF Dopant Location (% Silver) and 10⁻² s-10⁻⁴ s 10 s-0.1 s Laser Sensitivity level (mmol/silver mole) D_(min) + D_(min) + D_(min) + D_(min) + Speed@ Part # K₄Fe(CN)₆ K₄Ru(CN)₆ K₃IrCl₆ 1.35 1.95 1.35 1.95 D = 2.2 Contrast 6.1 50-99% — 93-95% 46.4 62.5+ −5.6 −4.3 197 1.667 0.025 0.00003 6.2 75-80% — 75-80% 51.1 61.8+ −4.1 −5.3 154 1.208 0.025 0.00003 6.3 50-99% — 93-95% 16.6 22.4 −2.3 −3.7 184 2.228 0.025 0.0004  6.4 75-80% — 75-80% 16.0 24.7 −3.6 −3.9 171 2.128 0.025 0.0004  6.5 — 50-99% 93-95% 83.6+ 66.7+ 0.3 1.8 154 1.278 0.025 0.00003 6.6 — 75-80% 75-80% 79.6+ 65.7+ 4.6 5.3 154 1.233 0.025 0.00003 6.7 — 50-99% 93-95% 30.1 69.8+ 0.5 0.2 162 1.763 0.040 0.0004  6.8 — 75-80% 75-80% 5.2 6.2 1.6 −3.2 226 2.702 (INV) 0.040 0.0004 

[0154] It evident from Table VI above that incorporation of a ruthenium dopant of Formula (I) and an iridium dopant, where the iridium dopant is present at a level of at least 10⁻⁷ mol/silver mole, in a common dopant band located between 70-90% of grain precipitation in a AgCl grain record improves HIRF, laser and optical sensitometric performance over a case where the dopants are added at different locations within a grain, where an iron dopant is used in place of the ruthenium dopant, or where the dopants are added in a common band within 70-90% of grain formation where the level of iridium dopant is less than 10⁻⁷ mol/silver mole.

Example 7

[0155] This example compares effects of combinations of formula I dopant K₄Ru(CN)₆ and iridium dopant K₂IrCl₆ on shoulder reciprocity failure in comparison to the use of a combination of K₄Fe(CN)₆ and K₂IrCl₆. Emulsions for Parts 7.1-7.8 were precipitated similarly as for Emulsion EM-1, except that K₂IrCl₆ and either K₄Ru(CN)₆ or K₄Fe(CN)₆ were added during grain formation in amounts and at locations as indicated in Table VII.

[0156] In each case, silver chloride cubic emulsions sensitized similarly as for Part 1.1 for the red color record were used. TABLE VII Optical sensitivity HIRF LIRF Dopant Location (% Silver) and 10⁻² s-10⁻⁴ s 10 s-0.1 s Laser Sensitivity level (mmol/silver mole) D_(min) + D_(min) + D_(min) + D_(min) + Speed@ Part # K₄Fe(CN)₆ K₄Ru(CN)₆ K₃IrCl₆ 1.35 1.95 1.35 1.95 D = 2.2 Contrast 7.1 50-99% — 93-95% 49.5 69.8+ −5.8 −4.8 163 1.532 0.025 0.00003 7.2 75-80% — 75-80% 48.6 66.6+ −2.0 −4.2 160 1.245 0.025 0.00003 7.3 50-99% — 93-95% 24.8 50.7+ −8.4 −9.3 162 2.072 0.025 0.0004  7.4 75-80% — 75-80% 22.9 49.7+ −3.4 −4.5 169 2.080 0.025 0.0004  7.5 — 50-99% 93-95% 51.4 77.0+ −5.7 −4.8 157 1.323 0.025 0.00003 7.6 — 75-80% 75-80% 51.2 69.5+ 2.6 3.1 155 1.293 0.025 0.00003 7.7 — 50-99% 93-95% 14.1 25.3 −0.9 −2.3 199 2.205 0.040 0.0004  7.8 — 75-80% 75-80% 2.7 2.9 −1.3 −2.3 218 2.788 (INV) 0.040 0.0004 

[0157] It evident from Table VII above that incorporation of a ruthenium dopant of Formula (I) and an iridium dopant, where the iridium dopant is present at a level of at least 10⁻⁷ mol/silver mole, in a common dopant band located between 70-90% of grain precipitation in a AgCl grain record improves HIRF, laser and optical sensitometric performance over a case where the dopants are added at different locations within a grain, where an iron dopant is used in place of the ruthenium dopant, or where the dopants are added in a common band within 70-90% of grain formation where the level of iridium dopant is less than 10⁻⁷ mol/silver mole.

[0158] It is specifically contemplated that emulsions in accordance with the invention may be sensitized with red, green, and blue sensitizing dyes and be incorporated in a color paper format as described in Example 4 of U.S. Pat. No. 5,783,373, incorporated by reference above.

[0159] The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention. 

What is claimed is:
 1. A radiation-sensitive emulsion comprised of silver halide grains (a) containing greater than 50 mole percent chloride, based on silver, (b) having greater than 50 percent of their surface area provided by {100} crystal faces, and (c) having a central portion accounting for up to 99 percent of total silver and containing a first dopant of Formula (I): [RuL₆]^(n)  (I) wherein n is −2, −3 or −4, and L₆ represents bridging ligands which can be independently selected, provided that at least four of the ligands are anionic ligands, and at least one of the ligands is a cyano ligand or a ligand more electronegative than a cyano ligand; and a second dopant comprising an iridium coordination complex having ligands each of which are more electropositive than a cyano ligand; wherein the first dopant and the second dopants are located together in a common dopant band in an interior shell region of the central portion of the silver halide grains that surrounds at least 70 percent of the silver and, with the more centrally located silver, accounts for 90 percent of the silver halide forming the grains, and wherein the second dopant is present in the silver halide grains in a concentration of at least 10⁻⁷ mole/mole of total silver.
 2. An emulsion according to claim 1, wherein the second dopant comprises an iridium coordination complex containing a thiazole or substituted thiazole ligand.
 3. An emulsion according to claim 2, wherein the second dopant satisfies the formula: [IrL¹ ₆]^(n′)  (II) wherein n′ is zero, −1, −2, −3 or −4; and L¹ ₆represents six bridging ligands which can be independently selected, provided that at least four of the ligands are anionic ligands, each of the ligands is more electropositive than a cyano ligand, and at least one of the ligands comprises a thiazole or substituted thiazole ligand.
 4. An emulsion according to claim 3 wherein at least one of the ligands of the second dopant is a halide ligand.
 5. An emulsion according to claim 3 wherein at least four of the ligands of the second dopant are halide ligands.
 6. An emulsion according to claim 3 wherein at least one of the ligands of the second dopant is a chloride ligand.
 7. An emulsion according to claim 3 wherein at least four of the ligands of the second dopant are chloride ligands.
 8. An emulsion according to claim 3 wherein the second dopant is an iridium coordination complex containing five halide ligands.
 9. An emulsion according to claim 1 wherein each of the bridging ligands of the dopant of Formula (I) are at least as electronegative as cyano ligands.
 10. An emulsion according to claim 9 wherein the second dopant is a iridium hexacoordination complex containing at least five halide ligands.
 11. An emulsion according to claim 10 wherein the second dopant is an iridium coordination complex containing five halide ligands and a thiazole or 5-methyl thiazole ligand.
 12. An emulsion according to claim 1 wherein the first dopant is [Ru(CN)₆]⁻⁴ and the second dopant is an iridium coordination complex containing five halide ligands and a thiazole or 5-methyl thiazole ligand.
 13. An emulsion according to claim 1, wherein the first dopant is present in a concentration of from 10⁻⁸ to 10⁻³ mole per mole of silver, and the second dopant is present in a concentration of from 10⁻⁷ to 10⁴ mole per mole of silver.
 14. An emulsion according to claim 13 wherein the first dopant is present in a concentration of from 10⁻⁷ to 10⁻⁴ mole per silver mole.
 15. An emulsion according to claim 13 wherein the second dopant is present in a concentration from 10⁻⁷ to 10⁻⁵ mole per silver mole.
 16. An emulsion according to claim 1 wherein the silver halide grains contain at least 70 mole percent chloride, based on silver.
 17. An emulsion according to claim 1 wherein the silver halide grains contain less than 5 mole percent iodide, based on silver.
 18. A photographic recording element comprising a support bearing at least one radiation-sensitive silver halide emulsion layer comprising an emulsion according to claim
 1. 19. An electronic printing method which comprises subjecting the radiation sensitive silver halide emulsion layer of a recording element according to claim 22 to actinic radiation of at least 10⁻⁴ ergs/cm² for up to 100μ seconds duration in a pixel-by-pixel mode.
 20. A method according to claim 19 wherein the pixels are exposed to actinic radiation of about 10⁻³ ergs/cm² to 10² ergs/cm².
 21. A method according to claim 19 wherein the exposure is up to 10μ seconds.
 22. A method according to claim 19 wherein the source of actinic radiation is a light emitting diode.
 23. A method according to claim 19 wherein the source of actinic radiation is a laser. 